1. Spectroscopic and Computational Studies of (µ-Oxo)(µ-1,2-peroxo)diiron(III) Complexes of Relevance to Nonheme Diiron Oxygenase Intermediates
- Author
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Adam T. Fiedler, Masahito Kodera, József Kaizer, Mark P. Mehn, Xiaopeng Shan, Jonathan R. Frisch, Stéphane Torelli, Lawrence Que, Department of chemistry, University of Minnesota, University of Minnesota [Twin Cities] (UMN), University of Minnesota System-University of Minnesota System, Singapore Institute of Manufacturing Technology (SIMTech), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire (DCM), Université Joseph Fourier - Grenoble 1 (UJF)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Inorganic, Analytical and Applied Chemistry - University of Geneva, Department of Inorganic, Analytical and Applied Chemistry, Department of moleclar science and technology - Doshisha University - Kyotanabe - Japan, Doshisha University [Kyoto], Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), and Université de Genève = University of Geneva (UNIGE)
- Subjects
Iron ,Resonance Raman spectroscopy ,Inorganic chemistry ,Substituent ,010402 general chemistry ,Crystallography, X-Ray ,Ligands ,Spectrum Analysis, Raman ,01 natural sciences ,Ferric Compounds ,Vibration ,Article ,Catalysis ,chemistry.chemical_compound ,symbols.namesake ,Molecule ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Carboxylate ,Physical and Theoretical Chemistry ,ComputingMilieux_MISCELLANEOUS ,Extended X-ray absorption fine structure ,Molecular Structure ,010405 organic chemistry ,Chemistry ,Aryl ,Spectrometry, X-Ray Emission ,Resonance (chemistry) ,0104 chemical sciences ,3. Good health ,Oxygen ,Crystallography ,Kinetics ,Spectrophotometry ,symbols ,Oxygenases ,Raman spectroscopy - Abstract
With the goal of gaining insight into the structures of peroxo intermediates observed for oxygen activating nonheme diiron enzymes, a series of metastable synthetic diiron(III)-peroxo complexes with [FeIII2(µ-O)(µ-1,2-O2)] cores has been characterized by X-ray absorption and resonance Raman spectroscopy. EXAFS analysis shows that this basic core structure gives rise to an Fe-Fe distance of ~3.15 A; the distance is decreased by 0.1 A upon introduction of an additional carboxylate bridge. In corresponding resonance Raman studies, vibrations arising from both the Fe-O-Fe and the Fe-O-O-Fe units can be observed. A change in the Fe-Fe distance affects the ν(O-O) mode, as well as the νsym(Fe-O-Fe) and the νasym(Fe-O-Fe) modes. Indeed a linear correlation can be discerned between the ν(O-O) frequency of a complex and its Fe-Fe distance among the subset of complexes with [FeIII2(µ-OR)(µ-1,2-O2)] cores (R = H, alkyl, aryl, or no substituent). These experimental studies are complemented by a normal coordinate analysis and DFT calculations.
- Published
- 2008